WO2020138710A1 - Process liquid for extreme ultraviolet lithography and pattern forming method using same - Google Patents

Abstract

The present invention relates to a process liquid for reducing the collapse level of photoresist patterns and the number of defects, which comprises polyhydroxystyrene and is used for an extreme ultraviolet light source. More specifically, the present invention relates to a process liquid for reducing the collapse level of photoresist patterns and the number of defects and a pattern forming method using same, the process liquid comprising 0.0001 to 1 weight% of an alkaline material; 0.0001 to 1 weight% of an anionic surfactant; and 98 to 99.9998 wt% of water.

Description

Process solution for extreme ultraviolet lithography and pattern formation method using same

In the present invention, in a photoresist pattern process using extreme ultraviolet light as a light source, a process solution for improving the decay level and reducing the number of defects in a photoresist pattern containing polyhydroxystyrene (polyhydxoystyrene) and a method for forming a photoresist pattern using the same It is about.

In general, semiconductors are manufactured by a lithography process that uses ultraviolet light in the wavelength range of 193nm, 248nm or 365nm as exposure light, and competition for each company to reduce the minimum line width (hereinafter referred to as CD: Critical Dimension) is fierce.

Accordingly, in order to form a finer pattern, a light source of a smaller wavelength band is required. Currently, lithography technology using an extreme ultraviolet (EUV, extreme ultra violet, 13.5nm wavelength) light source is actively used, and a finer wavelength can be realized by using the light source. It became possible.

However, since the etch resistance of the photoresist for extreme ultraviolet rays is still not improved, a photoresist pattern having a large aspect ratio is continuously required, and as a result, pattern collapse easily occurs during development and the number of defects increases, thereby increasing the process margin in the manufacturing process. This greatly shrinking problem is occurring.

Accordingly, there is a need to develop a technique for improving the level of collapse generated during fine pattern formation and reducing the number of defects. In order to improve the pattern collapse level and reduce the number of defects, it may be best to improve the performance of the photoresist, but the development of a photoresist that satisfies all performance is difficult to ignore.

Although the need for new development of photoresist remains, efforts are being made to improve the level of pattern collapse and reduce the number of defects in other ways.

An object of the present invention is to develop a process liquid composition for improving the collapse level of a pattern generated after photoresist development and reducing the number of defects in a fine pattern process using extreme ultraviolet rays and a method for forming a photoresist pattern using the same.

Various surfactants are used in the aqueous-based process solution used during the development process, but an effective process solution was prepared using an anionic surfactant in the present invention.

When a non-ionic surfactant that is close to hydrophobicity is used in an aqueous-based process solution mainly using ultrapure water, it is possible to induce hydrophobicity of the photoresist wall surface to induce pattern melting and decay, but non-ionic surfactants There is a possibility that the property of the process liquid is not uniform due to a strong tendency to clump, and a defect may be caused by the clumped nonionic surfactant during use. That is, when using a nonionic surfactant, the amount of use must be increased to improve the melting, which may cause damage to the photoresist. In addition, in case of excessive use of an inappropriate surfactant for the purpose of lowering the surface tension of the process liquid in order to reduce the capillary force, the pattern may be further induced by inducing melting of the pattern.

In addition, in the case of cationic surfactants, metals are rarely guaranteed as the active groups dissociate into cations in aqueous solutions. This may cause a serious defect in the photolithography process.

In the present invention, it was confirmed that by using an anionic surfactant, the effect of improving pattern collapse and reducing the number of defects is excellent. This was found to be a result of being helpful in forming a fine pattern because the hydrophilic part is dissociated as an anion compared to a nonionic surfactant, and thus it is relatively easy to react with a portion having a + charge due to unreacted with the deprotected part in the photoresist.

Currently, a typical developer used in most photolithography development processes. Based on pure water, tetramethylammonium hydroxide is used at a certain concentration (in most processes, 2.38% by weight of tetramethylammonium hydroxide and 97.62% by weight of water are used in combination). Dilution), and even in the extreme ultraviolet lithography process, tetramethylammonium hydroxide is diluted in pure water and used as a developer.

During the extreme ultraviolet lithography process, the pattern collapse was confirmed when washed with pure water continuously after development, and even when the process solution containing tetramethylammonium hydroxide in pure water was applied continuously after development or applied continuously after pure water The collapse was confirmed.

In the case of a process solution containing tetramethylammonium hydroxide, it can be estimated that the fine pattern exposed with extreme ultraviolet light is weakened, and the capillary force is large or non-uniform to break the pattern.

Therefore, in order to improve the collapse of the pattern exposed to extreme ultraviolet rays and additionally to improve the line width roughness (LWR) and defects of the photoresist pattern required in the extreme ultraviolet process, the force exerted on the relatively exposed pattern than tetramethylammonium hydroxide is applied. It is necessary to review weak alkaline substances.

In the present invention, it was confirmed that when using tetraethylammonium hydroxide, tetrapropylammonium hydroxide, or tetrabutylammonium hydroxide among alkali materials, LWR or defects were improved, including pattern collapse.

Accordingly, the present invention is a preferred first embodiment, anionic surfactant 0.0001 to 1% by weight; 0.0001 to 1% by weight of an alkaline substance; And 98 to 99.9998% by weight of water, to provide a process solution for improving the decay level and reducing the number of defects in the photoresist pattern generated during photoresist development.

The anionic surfactant according to the embodiment may be selected from the group consisting of polycarboxylate, sulfonate, sulfate ester salt, phosphate ester salt, or mixtures thereof.

The alkali material according to the embodiment may be selected from the group consisting of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or mixtures thereof.

The present invention further comprises: (a) applying a photoresist to a semiconductor substrate and forming a film; (b) exposing and developing the photoresist film to form a pattern; And (c) washing the photoresist pattern with a process solution for improving the decay level and reducing the number of defects in the photoresist pattern.

The cause of the pattern collapse is thought to be due to the capillary force generated between the patterns when the pattern is washed with pure water after development, but empirically knows that reducing only the capillary force cannot completely improve the pattern collapse and reduce the number of defects. Could.

In the case of excessive use of an inappropriate surfactant for the purpose of lowering the surface tension of the process liquid to reduce the capillary force, the pattern may be melted or the number of defects may be increased.

In order to improve the pattern collapse and reduce the number of defects, it is important to select a surfactant that reduces the surface tension of the process solution and prevents the melting of the photoresist pattern.

The process solution of the present invention exerts an excellent effect on a photoresist using an extreme ultraviolet light source, and in particular, a pattern generated during the development of a photoresist whose main component of the photoresist is polyhydroxystyrene. It has the effect of improving the level of collapse and reducing the number of defects.

The process solution of the present invention has an effect of improving the collapse level of a pattern and reducing the number of defects, which is an effect that photoresist alone cannot achieve when forming a pattern using an extreme ultraviolet light source. The method of forming a photoresist pattern included includes an effect of significantly reducing production costs.

Hereinafter, the present invention will be described in more detail.

The present invention, developed through numerous studies over a long period of time, is "an alkali material selected from the group consisting of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or mixtures thereof 0.0001 to 1 Weight %; 0.0001 to 1% by weight of anionic surfactants selected from the group consisting of polycarboxylates, sulfonic acid salts, sulfate ester salts, phosphate ester salts or mixtures thereof; and photo containing 98 to 99.9998% by weight of water The process pattern for improving the decay level of the resist pattern and reducing the number of defects", and the composition components and composition ratios of the process liquids of the present invention are set as Examples 1 to 40 to compare the composition components and composition ratios in contrast thereto. It was set as 1 to Comparative Example 22.

Hereinafter, preferred embodiments of the present invention and comparative examples for comparison therewith will be described. However, the following examples are only one preferred embodiment of the present invention, and the present invention is not limited to the following examples.

[Example 1]

A process solution for improving the decay level of the photoresist pattern containing 0.0001% by weight of polyammonium ammonium salt and 0.01% by weight of tetrabutylammonium hydroxide was prepared by the following method.

0.0001% by weight of polyammonium ammonium salt and 0.01% by weight of tetrabutylammonium hydroxide were added to the remaining amount of distilled water, stirred for 5 hours, and then passed through a 0.01um filter to remove fine solid impurities, and the level of collapse of the photoresist pattern A process solution was prepared to improve.

[Example 2 to Example 40]

According to the composition as described in Table 1 to Table 12, a process solution for improving the defect level of the same photoresist pattern as in Example 1 was prepared.

[Comparative Example 1]

In general, distilled water used as the last cleaning solution in the developing process during the semiconductor device manufacturing process was prepared.

[Comparative Example 2 ~ Comparative Example 22]

According to the composition as described in Table 1 to Table 12, a process solution was prepared as in Example 1 for comparison with the Examples.

[Experimental Example 1 to Experimental Example 40, Comparative Experimental Example 1 to Comparative Experimental Example 22]

In Example 1 to Example 40 and Comparative Example 1 to Comparative Example 22, the pattern collapse level and the number of defects were reduced for the patterned silicon wafer to measure Experimental Example 1 to Experimental Example 40, Comparative Experimental Example 1 to Comparative Experimental Example 22, and the results are shown in Tables 13 and 14.

(1) Confirmation of pattern collapse prevention

After splitting the exposure energy and focus, the number of blocks in which the pattern does not collapse out of 89 total blocks was measured using a critical dimension-scanning electron microscope (CD-SEM, Hitachi).

(2) Defect reduction ratio

Defect number (A) was measured for the photoresist pattern rinsed with each process liquid sample using a surface defect observation device (manufactured by KLA Tencor), and the rinse treatment was performed using pure water only. It was expressed as a percentage (%) of the number of defects (B) in one case, that is, (A/B)X100.

The number of defects after treatment with pure water was defined as 100, and the degree of reduction (improvement) or increase (deterioration) compared to the number of defects treated with pure water was expressed as a reduction ratio.

(3) Transparency

The transparency of the prepared process solution was visually confirmed and displayed as transparent or opaque.

	Surfactants		Alkali substance		Distilled water
	designation	Content (% by weight)	designation	Content (% by weight)	designation	Content (% by weight)
Example 1	Polycarboxylic acid ammonium salt	0.0001	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9899
Example 2	Polycarboxylic acid ammonium salt	0.001	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9890
Example 3	Polycarboxylic acid ammonium salt	0.01	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9800
Example 4	Polycarboxylic acid ammonium salt	0.1	Tetrabutylammonium hydroxide	0.01	Distilled water	99.8900
Example 5	Polycarboxylic acid ammonium salt	One	Tetrabutylammonium hydroxide	0.01	Distilled water	98.9900
Comparative Example 1	-	-	-	-	Distilled water	100
Comparative Example 2	-	-	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9900
Comparative Example 3	Polycarboxylic acid ammonium salt	2	Tetrabutylammonium hydroxide	0.01	Distilled water	97.9900

	Surfactants		Alkali substance		Distilled water
	designation	Content (% by weight)	designation	Content (% by weight)	designation	Content (% by weight)
Example 6	Sulfonate	0.0001	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9899
Example 7	Sulfonate	0.001	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9890
Example 8	Sulfonate	0.01	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9800
Example 9	Sulfonate	0.1	Tetrabutylammonium hydroxide	0.01	Distilled water	99.8900
Example 10	Sulfonate	One	Tetrabutylammonium hydroxide	0.01	Distilled water	98.9900
Comparative Example 1	-	-	-	-	Distilled water	100
Comparative Example 2	-	-	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9900
Comparative Example 4	Sulfonate	2	Tetrabutylammonium hydroxide	0.01	Distilled water	97.9900

	Surfactants		Alkali substance		Distilled water
	designation	Content (% by weight)	designation	Content (% by weight)	designation	Content (% by weight)
Example 11	Sulfate ester salt	0.0001	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9899
Example 12	Sulfate ester salt	0.001	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9890
Example 13	Sulfate ester salt	0.01	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9800
Example 14	Sulfate ester salt	0.1	Tetrabutylammonium hydroxide	0.01	Distilled water	99.8900
Example 15	Sulfate ester salt	One	Tetrabutylammonium hydroxide	0.01	Distilled water	98.9900
Comparative Example 1	-	-	-	-	Distilled water	100
Comparative Example 2	-	-	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9900
Comparative Example 5	Sulfate ester salt	2	Tetrabutylammonium hydroxide	0.01	Distilled water	97.9900

	Surfactants		Alkali substance		Distilled water
	designation	Content (% by weight)	designation	Content (% by weight)	designation	Content (% by weight)
Example 16	Phosphate ester salt	0.0001	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9899
Example 17	Phosphate ester salt	0.001	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9890
Example 18	Phosphate ester salt	0.01	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9800
Example 19	Phosphate ester salt	0.1	Tetrabutylammonium hydroxide	0.01	Distilled water	99.8900
Example 20	Phosphate ester salt	One	Tetrabutylammonium hydroxide	0.01	Distilled water	98.9900
Comparative Example 1	-	-	-	-	Distilled water	100
Comparative Example 2	-	-	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9900
Comparative Example 6	Phosphate ester salt	2	Tetrabutylammonium hydroxide	0.01	Distilled water	97.9900

	Surfactants		Alkali substance		Distilled water
	designation	Content (% by weight)	designation	Content (% by weight)	designation	Content (% by weight)
Example 21	Polycarboxylic acid ammonium salt	0.01	Tetrabutylammonium hydroxide	0.0001	Distilled water	99.9899
Example 22	Polycarboxylic acid ammonium salt	0.01	Tetrabutylammonium hydroxide	0.001	Distilled water	99.9890
Example 3	Polycarboxylic acid ammonium salt	0.01	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9800
Example 23	Polycarboxylic acid ammonium salt	0.01	Tetrabutylammonium hydroxide	0.1	Distilled water	99.8900
Example 24	Polycarboxylic acid ammonium salt	0.01	Tetrabutylammonium hydroxide	One	Distilled water	98.9900
Comparative Example 7	Polycarboxylic acid ammonium salt	0.01	-	-	Distilled water	99.9900
Comparative Example 8	Polycarboxylic acid ammonium salt	0.01	Tetrabutylammonium hydroxide	2	Distilled water	97.9900

	Surfactants		Alkali substance		Distilled water
	designation	Content (% by weight)	designation	Content (% by weight)	designation	Content (% by weight)
Example 25	Sulfonate	0.01	Tetrabutylammonium hydroxide	0.0001	Distilled water	99.9899
Example 26	Sulfonate	0.01	Tetrabutylammonium hydroxide	0.001	Distilled water	99.9890
Example 8	Sulfonate	0.01	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9800
Example 27	Sulfonate	0.01	Tetrabutylammonium hydroxide	0.1	Distilled water	99.8900
Example 28	Sulfonate	0.01	Tetrabutylammonium hydroxide	One	Distilled water	98.9900
Comparative Example 9	Sulfonate	0.01	-	-	Distilled water	99.9900
Comparative Example 10	Sulfonate	0.01	Tetrabutylammonium hydroxide	2	Distilled water	97.9900

	Surfactants		Alkali substance		Distilled water
	designation	Content (% by weight)	designation	Content (% by weight)	designation	Content (% by weight)
Example 29	Sulfate ester salt	0.01	Tetrabutylammonium hydroxide	0.0001	Distilled water	99.9899
Example 30	Sulfate ester salt	0.01	Tetrabutylammonium hydroxide	0.001	Distilled water	99.9890
Example 13	Sulfate ester salt	0.01	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9800
Example 31	Sulfate ester salt	0.01	Tetrabutylammonium hydroxide	0.1	Distilled water	99.8900
Example 32	Sulfate ester salt	0.01	Tetrabutylammonium hydroxide	One	Distilled water	98.9900
Comparative Example 11	Sulfate ester salt	0.01	-	-	Distilled water	99.9900
Comparative Example 12	Sulfate ester salt	0.01	Tetrabutylammonium hydroxide	2	Distilled water	97.9900

	Surfactants		Alkali substance		Distilled water
	designation	Content (% by weight)	designation	Content (% by weight)	designation	Content (% by weight)
Example 33	Phosphate ester salt	0.01	Tetrabutylammonium hydroxide	0.0001	Distilled water	99.9899
Example 34	Phosphate ester salt	0.01	Tetrabutylammonium hydroxide	0.001	Distilled water	99.9890
Example 18	Phosphate ester salt	0.01	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9800
Example 35	Phosphate ester salt	0.01	Tetrabutylammonium hydroxide	0.1	Distilled water	99.8900
Example 36	Phosphate ester salt	0.01	Tetrabutylammonium hydroxide	One	Distilled water	98.9900
Comparative Example 13	Phosphate ester salt	0.01	-	-	Distilled water	99.9900
Comparative Example 14	Phosphate ester salt	0.01	Tetrabutylammonium hydroxide	2	Distilled water	97.9900

	Surfactants		Alkali substance		Distilled water
	designation	Content (% by weight)	designation	Content (% by weight)	designation	Content (% by weight)
Example 3	Polycarboxylic acid ammonium salt	0.01	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9800
Example 37	Polycarboxylic acid ammonium salt	0.01	Tetraethylammonium hydroxide	0.01	Distilled water	99.9800
Comparative Example 15	Polycarboxylic acid ammonium salt	0.01	Tetramethylammonium hydroxide	0.01	Distilled water	99.9800
Comparative Example 16	Polycarboxylic acid ammonium salt	0.01	Tetrapentylammonium hydroxide	0.01	Distilled water	99.9800

	Surfactants		Alkali substance		Distilled water
	designation	Content (% by weight)	designation	Content (% by weight)	designation	Content (% by weight)
Example 8	Sulfonate	0.01	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9800
Example 38	Sulfonate	0.01	Tetraethylammonium hydroxide	0.01	Distilled water	99.9800
Comparative Example 17	Sulfonate	0.01	Tetramethylammonium hydroxide	0.01	Distilled water	99.9800
Comparative Example 18	Sulfonate	0.01	Tetrapentylammonium hydroxide	0.01	Distilled water	99.9800

	Surfactants		Alkali substance		Distilled water
	designation	Content (% by weight)	designation	Content (% by weight)	designation	Content (% by weight)
Example 13	Sulfate ester salt	0.01	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9800
Example 39	Sulfate ester salt	0.01	Tetraethylammonium hydroxide	0.01	Distilled water	99.9800
Comparative Example 19	Sulfate ester salt	0.01	Tetramethylammonium hydroxide	0.01	Distilled water	99.9800
Comparative Example 20	Sulfate ester salt	0.01	Tetrapentylammonium hydroxide	0.01	Distilled water	99.9800

	Surfactants		Alkali substance		Distilled water
	designation	Content (% by weight)	designation	Content (% by weight)	designation	Content (% by weight)
Example 18	Phosphate ester salt	0.01	Tetrabutylammonium hydroxide	0.01	Distilled water	99.9800
Example 40	Phosphate ester salt	0.01	Tetraethylammonium hydroxide	0.01	Distilled water	99.9800
Comparative Example 21	Phosphate ester salt	0.01	Tetramethylammonium hydroxide	0.01	Distilled water	99.9800
Comparative Example 22	Phosphate ester salt	0.01	Tetrapentylammonium hydroxide	0.01	Distilled water	99.9800

[Experimental Example 1 to Experimental Example 40, Comparative Experimental Example 1 to Comparative Experimental Example 22]

In Example 1 to Example 40 and Comparative Example 1 to Comparative Example 22, the pattern collapse level, the number of defects, and the transparency of the patterned silicon wafer were measured to measure Experimental Examples 1 to 40 and Comparative Experimental Examples 1 to It was shown as Experimental Example 22, and the results are shown in Tables 13 and 14.

(1) Pattern collapse level

After splitting the exposure energy and focus, the number of blocks in which the pattern does not collapse out of 89 total blocks was measured using a critical dimension-scanning electron microscope (CD-SEM, Hitachi).

(2) Number of defects

Defect number (A) was measured for the photoresist pattern rinsed with each process liquid sample using a surface defect observation device (manufactured by KLA Tencor), and the rinse treatment was performed using pure water only. It was expressed as a percentage (%) of the number of defects (B) in one case, that is, (A/B)X100.

(3) Transparency

The transparency of the prepared process solution was visually confirmed and displayed as transparent or opaque.

	Number of blocks without pattern collapse	Defect reduction ratio (%)	transparency
Experimental Example 1	55	53	Transparency
Experimental Example 2	63	46	Transparency
Experimental Example 3	81	25	Transparency
Experimental Example 4	64	35	Transparency
Experimental Example 5	68	80	Transparency
Experimental Example 6	53	52	Transparency
Experimental Example 7	61	48	Transparency
Experimental Example 8	76	30	Transparency
Experimental Example 9	65	36	Transparency
Experimental Example 10	67	75	Transparency
Experimental Example 11	52	56	Transparency
Experimental Example 12	64	47	Transparency
Experimental Example 13	75	31	Transparency
Experimental Example 14	62	38	Transparency
Experimental Example 15	66	72	Transparency
Experimental Example 16	52	56	Transparency
Experimental Example 17	68	50	Transparency
Experimental Example 18	76	33	Transparency
Experimental Example 19	65	38	Transparency
Experimental Example 20	69	78	Transparency
Experimental Example 21	70	81	Transparency
Experimental Example 22	72	53	Transparency
Experimental Example 23	75	38	Transparency
Experimental Example 24	66	84	Transparency
Experimental Example 25	69	80	Transparency
Experimental Example 26	70	52	Transparency
Experimental Example 27	71	40	Transparency
Experimental Example 28	65	87	Transparency
Experimental Example 29	72	76	Transparency
Experimental Example 30	70	50	Transparency
Experimental Example 31	76	37	Transparency
Experimental Example 32	68	88	Transparency
Experimental Example 33	67	80	Transparency
Experimental Example 34	71	52	Transparency
Experimental Example 35	72	40	Transparency
Experimental Example 36	66	86	Transparency
Experimental Example 37	57	69	Transparency
Experimental Example 38	59	70	Transparency
Experimental Example 39	55	71	Transparency
Experimental Example 40	60	65	Transparency

	Number of blocks without pattern collapse	Defect reduction ratio (%)	transparency
Comparative Experimental Example 1	46	100	Transparency
Comparative Experimental Example 2	40	95	Transparency
Comparative Experimental Example 3	37	276	opacity
Comparative Experimental Example 4	38	269	opacity
Comparative Experimental Example 5	36	274	opacity
Comparative Experimental Example 6	35	281	opacity
Comparative Experimental Example 7	58	127	Transparency
Comparative Experimental Example 8	41	157	Transparency
Comparative Experimental Example 9	59	129	Transparency
Comparative Experimental Example 10	39	160	Transparency
Comparative Experimental Example 11	57	124	Transparency
Comparative Experimental Example 12	40	159	Transparency
Comparative Experimental Example 13	59	120	Transparency
Comparative Experimental Example 14	42	151	Transparency
Comparative Experimental Example 15	52	142	Transparency
Comparative Experimental Example 16	50	99	Transparency
Comparative Experimental Example 17	49	140	Transparency
Comparative Experimental Example 18	51	101	Transparency
Comparative Experimental Example 19	54	138	Transparency
Comparative Experimental Example 20	49	97	Transparency
Comparative Experimental Example 21	53	151	Transparency
Comparative Experimental Example 22	50	98	Transparency

As a result of comparing Experimental Example 1 to Experimental Example 40 and Comparative Experimental Example 1 to Comparative Experimental Example 22, based on Comparative Experimental Example 1, if the number of blocks without pattern collapse is 50 or more and the defect number reduction ratio is 90% or less, the improved excellent result It was able to reveal what it represents.

0.0001 to 1% by weight of anionic surfactants selected from polycarboxylates, sulfonates, sulfate ester salts and phosphate ester salts, which are process solutions corresponding to Experimental Examples 1 to 40; 0.0001 to 1% by weight of an alkali material selected from tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide; And in the case of a process solution containing 98 to 99.9998% by weight of water, when compared with Comparative Experimental Example 1 to Comparative Experimental Example 22, it was confirmed that the pattern collapse level was improved and the number of defects was also improved.

In particular, Experimental Examples 2 to 4, Experimental Examples 7 to 9, Experimental Examples 12 to 14, Experimental Examples 17 to 19, Experimental Examples 22 and 23, Experimental Examples 26 and 27, Experimental Examples 30 and 31, and Experimental Examples 34 and 35 It was confirmed that the case showed more desirable results.

That is, Experimental Examples 2 to 4, Experimental Examples 7 to 9, Experimental Examples 12 to 14, Experimental Examples 17 to 19, Experimental Examples 22, 23, Experimental Examples 26, 27, Experimental Examples 30, 31, and Experimental Examples 34 and 35 0.001 to 0.1% by weight of an anionic surfactant selected from polycarboxylate, sulfonate, sulfate ester, and phosphate ester salts, which are the corresponding process solutions; 0.001 to 0.1% by weight of an alkali material selected from tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide; And 99.8 to 99.998% by weight of water; for the process solution for improving the decay level of the photoresist pattern and reducing the number of defects, as well as when compared with comparative experiments, as well as when compared with other experimental examples, Since it was confirmed that the level of pattern collapse was improved and the number of defects was also improved, this concentration range was confirmed to be more desirable.

As a result of evaluating the collapse level of the photoresist pattern according to Example 3, the number of blocks in which pattern collapse did not occur was measured to be 81.

As a result of evaluating the collapse level of the photoresist pattern according to Comparative Experimental Example 1, the number of blocks in which pattern collapse did not occur was measured to be 46.

Since the specific parts of the present invention have been described in detail above, it will be apparent to those skilled in the art that this specific technique is only a preferred embodiment, and the scope of the present invention is not limited thereby. . Therefore, the substantial scope of the present invention will be defined by the claims and their equivalents.

Claims (12)

1. In the process solution for improving the decay level and reducing the number of defects in a photoresist pattern containing polyhydoxystyrene in a photoresist pattern process using extreme ultraviolet light as a light source,

   0.0001 to 1% by weight of anionic surfactant;

   0.0001 to 1% by weight of an alkaline substance; And

   98 to 99.9998% by weight; Process solution for improving the decay level and reducing the number of defects of the photoresist pattern, characterized by comprising.
2. The method of claim 1, wherein the anionic surfactant is selected from the group consisting of polycarboxylates, sulfonate salts, sulfate ester salts, phosphate ester salts, or mixtures thereof. Process solution for reducing water.
3. The process solution for improving the decay level and reducing the number of defects in a photoresist pattern according to claim 2, wherein the anionic surfactant is polycarboxylate.
4. The process solution for improving the decay level and reducing the number of defects in a photoresist pattern according to claim 2, wherein the anionic surfactant is a sulfonate salt.
5. The process solution for improving the collapse level of a photoresist pattern and reducing the number of defects according to claim 2, wherein the anionic surfactant is a sulfate ester salt.
6. The process solution for improving the decay level of a photoresist pattern and reducing the number of defects according to claim 1, wherein the anionic surfactant is a phosphate ester salt.
7. The decay level of the photoresist pattern according to claim 1, wherein the alkali material is selected from the group consisting of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or mixtures thereof. Process fluid for improvement and reduction of defects.
8. The process of claim 7, wherein the alkali material is selected from the group consisting of tetraethylammonium hydroxide, tetrabutylammonium hydroxide, or mixtures thereof. liquid.
9. The process solution for improving the decay level of a photoresist pattern and reducing the number of defects according to claim 8, wherein the alkali material is tetraethylammonium hydroxide.
10. The process solution for improving the decay level of a photoresist pattern and reducing the number of defects according to claim 8, wherein the alkali material is tetrabutylammonium hydroxide.
11. The method according to any one of claims 1 to 10,

    0.001 to 0.1% by weight of anionic surfactant;

    0.001 to 0.1% by weight of an alkaline substance; And

    99.8 to 99.998% by weight of water; Process solution for improving the decay level and reducing the number of defects of the photoresist pattern, characterized in that it comprises.
12. (a) applying a photoresist to a semiconductor substrate and forming a film;

    (b) exposing the photoresist film to extreme ultraviolet rays and developing the pattern to form a pattern; And

    (c) washing the photoresist pattern with a process solution for improving the decay level and reducing the number of defects of the photoresist pattern of any one of claims 1 to 10; .